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Antiferromagnetic Interactions in Copper(II) µ-Oxalato Dinuclear Complexes: The Role of the Counterion

Julve, Miguel and Gleizes, Alain and Chamoreau, Lise Marie and Ruiz, Eliseo and Verdaguer, Michel Antiferromagnetic Interactions in Copper(II) µ-Oxalato Dinuclear Complexes: The Role of the Counterion. (2018) European Journal of Inorganic Chemistry, 2018 (3-4). 509-516. ISSN 1434-1948

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Official URL: https://doi.org/10.1002/ejic.201700935


We report the preparation, crystal structure determination, magnetic properties and DFT calculations of five oxalato‐bridged dicopper(II) complexes of formula [Cu2(bpy)2(H2O)2(C2O4)](CF3SO3)2 (1), [Cu2(bpy)2(C2O4)](PF6)2 (2), [Cu2(bpy)2(C2O4)](ClO4)2 (3), [Cu2(bpy)2Cl2(C2O4)]·H2O (4) and [Cu2(bpy)2(NO2)2(C2O4)] (5) (bpy = 2,2′‐bipyridine and C2O42– = oxalate). Compounds 1, 2, 4 and 5 crystallize in the monoclinic system and 3 crystallizes in the triclinic system. The oxalate ligands in 1–5 adopt the bis‐bidentate coordination mode and the two bpy molecules act as terminal ligands. The coordination of the counterions and the surroundings of the copper(II) ions differentiate the five compounds. The four nearest neighbours of copper(II) in 1–4 are roughly in the plane of the CuC2O4Cu framework, whereas they are in an almost perpendicular plane in 5. Using the isotropic Hamiltonian H = –J S1·S2, where S1 and S2 are the spin quantum operators for Cu1 and Cu2; J is –384 cm–1 for 1, –392 cm–1 for 2 and –387 cm–1 for 3, slightly decreasing to –328 cm–1 for 4 and falling to –14 cm–1 for 5. The influence of the anions on the magnetic properties of this family of compounds is explained by the changes in the overlap of the magnetic orbitals through the oxalate bridge. DFT calculations reproduce well the experimental values of J and provide an illustration of the magnetic orbitals

Item Type:Article
Audience (journal):International peer-reviewed journal
Uncontrolled Keywords:
Institution:French research institutions > Centre National de la Recherche Scientifique - CNRS (FRANCE)
Université de Toulouse > Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Other partners > Sorbonne Université (FRANCE)
Université de Toulouse > Université Toulouse III - Paul Sabatier - UT3 (FRANCE)
Other partners > Universitat de Barcelona - UB (SPAIN)
Other partners > Universitat de Valencia - UV (SPAIN)
Laboratory name:
Deposited On:27 Mar 2019 09:38

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